Crystal structure of ethyl 4-[(1H-pyrazol-1-yl)meth­yl]benzoate

Wang, J.-X.; Feng, C.

doi:10.1107/S1600536814025100

organic compounds

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Volume 70| Part 12| December 2014| Page o1287

doi:10.1107/S1600536814025100

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Crystal structure of ethyl 4-[(1H-pyrazol-1-yl)methyl]benzoate

Ju-Xian Wang ^a and Chao Feng ^b ^*

^aInstitute of Medicinal Biotechnology, Chinese Academy of Medical Sciences and Peking Union Medical College, Beijing 100050, People's Republic of China, and ^bSchool of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: fchg042@163.com

Edited by W. T. A. Harrison, University of Aberdeen, Scotland (Received 15 November 2014; accepted 16 November 2014; online 26 November 2014)

In the title molecule, C₁₃H₁₄N₂O₂, the dihedral angle between the pyrazole and benzene ring mean planes is 76.06 (11)°, and the conformation of the ethyl side chain is anti [C—O—C—C = −175.4 (3)°]. In the crystal, the only directional interactions are very weak C—H ⋯π interactions involving both the pyrazole and benzene rings, leading to the formation of a three-dimensional network.

Keywords: crystal structure; ester; pyrazole derivative.

CCDC reference: 1034364

1. Related literature

For a related structure, see: Dong et al. (2011 ). For background to the properties of pyrazole derivatives, see: Adnan & Tarek (2004 ); Ashraf et al. (2003 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₄N₂O₂
M_r = 230.26
Triclinic, $[P \overline 1]$
a = 8.1338 (12) Å
b = 8.1961 (9) Å
c = 10.7933 (11) Å
α = 74.013 (9)°
β = 83.308 (10)°
γ = 64.734 (13)°
V = 625.54 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 293 K
0.22 × 0.20 × 0.18 mm

2.2. Data collection

Agilent SuperNova (Single source at offset, Eos) diffractometer
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012 ) T_min = 0.982, T_max = 0.985
4295 measured reflections
2197 independent reflections
1639 reflections with I > 2σ(I)
R_int = 0.032

2.3. Refinement

R[F² > 2σ(F²)] = 0.067
wR(F²) = 0.201
S = 1.15
2197 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.18 e Å⁻³
Δρ_min = −0.23 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the N1/N2/C1–C3 and C5–C10 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2⋯Cg2ⁱ	0.93	2.94	3.670 (4)	137
C4—H4A⋯Cg1ⁱⁱ	0.97	3.00	3.600 (3)	122
C12—H12A⋯Cg2ⁱⁱⁱ	0.97	2.82	3.689 (4)	150
Symmetry codes: (i) x-1, y, z; (ii) -x, -y, -z; (iii) -x, -y+1, -z+1.

Data collection: FRAMBO (Bruker, 2004 ); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 1034364

Crystal structure: contains datablocks I, New_Global_Publ_Block. DOI: 10.1107/S1600536814025100/hb7319sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536814025100/hb7319Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536814025100/hb7319Isup3.cml

checkCIF report

Comment top

Pyrazole and its derivatives are an important class of N-heterocyclic compounds because they exhibit a broad spectrum of pharmacological activities such as antifungal (Adnan & Tarek, 2004), antitumor and antiangiogenic activities (Ashraf et al., 2003). As part of pyrazole derivatives, the crystal structure of 1, 4-bis[(1H-pyrazol-1-yl)methyl]benzene has been determined (Dong et al., 2011). As part of this ongoing search for new pyrazole compounds, the title compound was synthesized and its crystal structure is reported herein. In the title compound (Fig. 1), bond lengths and angles fall in normal ranges. The dihedral angle between the pyrazole ring (N1/N2/C1—C3) and the phenyl ring (C5—C10) is 76.06 (11) °. In the crystal, there exists weak C–H···π contacts.

Related literature top

For a related structure, see: Dong et al. (2011). For background to the properties of pyrazole derivatives, see: Adnan & Tarek (2004); Ashraf et al. (2003).

Experimental top

In a 250 ml four-necked round-bottom flask equipped with a mechanical stirrer, pyrazole (0.680 g 10 mmol), potassium carbonate (2.073 g 15 mmol) and 1-(4-(bromomethyl)phenyl)-1-hydroxypentan-2-one (2.712 g, 10 mmol) were cautiously dissolved in acetone (100 ml). The solution was heated at 65 °C for 6 h, then the mixture was filtered off was removed by rotatory evaporator at 35 °C and the crude product was obtained 1.815 g (66.1%). Colourless blocks of the title compound were obtained from ethanol by slow evaporation.

Computing details top

Data collection: FRAMBO (Bruker, 2004); cell refinement: SAINT (Bruker, 2004); data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level.

View of the packing diagram of the title compound along the b axis.

Ethyl 4-[(1H-pyrazol-1-yl)methyl]benzoate top

Crystal data top

C₁₃H₁₄N₂O₂	Z = 2
M_r = 230.26	F(000) = 244
Triclinic, P1	D_x = 1.222 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.1338 (12) Å	Cell parameters from 1485 reflections
b = 8.1961 (9) Å	θ = 4.3–28.2°
c = 10.7933 (11) Å	µ = 0.08 mm⁻¹
α = 74.013 (9)°	T = 293 K
β = 83.308 (10)°	Block, colourless
γ = 64.734 (13)°	0.22 × 0.20 × 0.18 mm
V = 625.54 (13) Å³

Data collection top

Agilent SuperNova (Single source at offset, Eos) diffractometer	2197 independent reflections
Radiation source: fine-focus sealed tube	1639 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 25.0°, θ_min = 3.0°
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	h = −9→9
T_min = 0.982, T_max = 0.985	k = −9→9
4295 measured reflections	l = −12→8

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.067	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.201	H-atom parameters constrained
S = 1.15	w = 1/[σ²(F_o²) + (0.079P)² + 0.2197P] where P = (F_o² + 2F_c²)/3
2197 reflections	(Δ/σ)_max < 0.001
155 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.23 e Å⁻³

Crystal data top

C₁₃H₁₄N₂O₂	γ = 64.734 (13)°
M_r = 230.26	V = 625.54 (13) Å³
Triclinic, P1	Z = 2
a = 8.1338 (12) Å	Mo Kα radiation
b = 8.1961 (9) Å	µ = 0.08 mm⁻¹
c = 10.7933 (11) Å	T = 293 K
α = 74.013 (9)°	0.22 × 0.20 × 0.18 mm
β = 83.308 (10)°

Data collection top

Agilent SuperNova (Single source at offset, Eos) diffractometer	2197 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	1639 reflections with I > 2σ(I)
T_min = 0.982, T_max = 0.985	R_int = 0.032
4295 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.067	0 restraints
wR(F²) = 0.201	H-atom parameters constrained
S = 1.15	Δρ_max = 0.18 e Å⁻³
2197 reflections	Δρ_min = −0.23 e Å⁻³
155 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	−0.3321 (5)	0.2354 (4)	0.0922 (3)	0.0772 (9)
H1	−0.4412	0.3219	0.0516	0.093*
C2	−0.3185 (4)	0.0903 (5)	0.1964 (3)	0.0787 (9)
H2	−0.4119	0.0606	0.2394	0.094*
C3	−0.1386 (4)	−0.0001 (4)	0.2228 (3)	0.0718 (9)
H3	−0.0841	−0.1068	0.2885	0.086*
C4	0.1384 (4)	0.0519 (4)	0.1369 (3)	0.0653 (8)
H4A	0.1766	0.0861	0.0486	0.078*
H4B	0.2091	−0.0805	0.1712	0.078*
C5	0.1753 (3)	0.1603 (4)	0.2163 (2)	0.0543 (7)
C6	0.2157 (4)	0.0834 (4)	0.3464 (3)	0.0610 (7)
H6	0.2269	−0.0374	0.3842	0.073*
C7	0.2396 (4)	0.1856 (4)	0.4205 (2)	0.0584 (7)
H7	0.2671	0.1326	0.5077	0.070*
C8	0.2227 (3)	0.3657 (3)	0.3656 (2)	0.0505 (6)
C9	0.1870 (4)	0.4413 (4)	0.2343 (3)	0.0573 (7)
H9	0.1784	0.5611	0.1959	0.069*
C10	0.1643 (4)	0.3379 (4)	0.1609 (3)	0.0588 (7)
H10	0.1413	0.3888	0.0731	0.071*
C11	0.2393 (4)	0.4838 (4)	0.4420 (3)	0.0561 (7)
C12	0.2906 (4)	0.5017 (5)	0.6500 (3)	0.0726 (9)
H12A	0.1747	0.6050	0.6552	0.087*
H12B	0.3805	0.5512	0.6164	0.087*
C13	0.3460 (6)	0.3720 (6)	0.7790 (4)	0.1028 (13)
H13A	0.2574	0.3219	0.8103	0.154*
H13B	0.3544	0.4378	0.8374	0.154*
H13C	0.4622	0.2722	0.7729	0.154*
N1	−0.0526 (3)	0.0895 (3)	0.13866 (19)	0.0554 (6)
N2	−0.1716 (4)	0.2383 (3)	0.0558 (2)	0.0741 (8)
O1	0.2758 (3)	0.3958 (3)	0.56635 (18)	0.0672 (6)
O2	0.2213 (3)	0.6418 (3)	0.3986 (2)	0.0823 (7)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.075 (2)	0.072 (2)	0.083 (2)	−0.0205 (17)	−0.0233 (17)	−0.0225 (17)
C2	0.070 (2)	0.088 (2)	0.079 (2)	−0.0365 (18)	0.0043 (16)	−0.0178 (18)
C3	0.078 (2)	0.075 (2)	0.0547 (17)	−0.0352 (17)	−0.0020 (14)	0.0029 (15)
C4	0.0684 (18)	0.083 (2)	0.0557 (17)	−0.0358 (16)	0.0119 (13)	−0.0318 (15)
C5	0.0541 (15)	0.0664 (17)	0.0469 (15)	−0.0276 (13)	0.0101 (11)	−0.0209 (12)
C6	0.0804 (19)	0.0549 (16)	0.0506 (16)	−0.0330 (14)	0.0032 (13)	−0.0109 (12)
C7	0.0788 (19)	0.0601 (16)	0.0391 (14)	−0.0336 (14)	0.0003 (12)	−0.0086 (12)
C8	0.0534 (14)	0.0530 (14)	0.0456 (14)	−0.0235 (12)	0.0016 (11)	−0.0114 (11)
C9	0.0660 (17)	0.0557 (15)	0.0489 (15)	−0.0289 (13)	−0.0030 (12)	−0.0035 (12)
C10	0.0630 (17)	0.0721 (18)	0.0404 (14)	−0.0305 (14)	0.0011 (11)	−0.0090 (13)
C11	0.0593 (16)	0.0558 (16)	0.0552 (16)	−0.0262 (13)	−0.0016 (12)	−0.0124 (13)
C12	0.079 (2)	0.082 (2)	0.072 (2)	−0.0358 (17)	−0.0023 (15)	−0.0388 (17)
C13	0.131 (3)	0.105 (3)	0.070 (2)	−0.031 (2)	−0.027 (2)	−0.039 (2)
N1	0.0692 (14)	0.0607 (13)	0.0401 (12)	−0.0296 (11)	−0.0015 (10)	−0.0136 (10)
N2	0.100 (2)	0.0673 (16)	0.0533 (14)	−0.0374 (14)	−0.0200 (13)	−0.0007 (12)
O1	0.0917 (15)	0.0665 (12)	0.0502 (12)	−0.0353 (11)	−0.0060 (10)	−0.0181 (9)
O2	0.1173 (19)	0.0621 (13)	0.0756 (15)	−0.0452 (13)	−0.0147 (13)	−0.0102 (11)

Geometric parameters (Å, º) top

C1—N2	1.327 (4)	C7—H7	0.9300
C1—C2	1.367 (5)	C8—C9	1.391 (3)
C1—H1	0.9300	C8—C11	1.487 (4)
C2—C3	1.351 (4)	C9—C10	1.385 (4)
C2—H2	0.9300	C9—H9	0.9300
C3—N1	1.333 (4)	C10—H10	0.9300
C3—H3	0.9300	C11—O2	1.200 (3)
C4—N1	1.448 (3)	C11—O1	1.336 (3)
C4—C5	1.524 (4)	C12—O1	1.460 (3)
C4—H4A	0.9700	C12—C13	1.481 (5)
C4—H4B	0.9700	C12—H12A	0.9700
C5—C10	1.381 (4)	C12—H12B	0.9700
C5—C6	1.385 (4)	C13—H13A	0.9600
C6—C7	1.386 (4)	C13—H13B	0.9600
C6—H6	0.9300	C13—H13C	0.9600
C7—C8	1.384 (4)	N1—N2	1.348 (3)

N2—C1—C2	112.2 (3)	C10—C9—C8	119.9 (2)
N2—C1—H1	123.9	C10—C9—H9	120.1
C2—C1—H1	123.9	C8—C9—H9	120.1
C3—C2—C1	104.4 (3)	C5—C10—C9	120.9 (2)
C3—C2—H2	127.8	C5—C10—H10	119.5
C1—C2—H2	127.8	C9—C10—H10	119.5
N1—C3—C2	108.4 (3)	O2—C11—O1	122.7 (3)
N1—C3—H3	125.8	O2—C11—C8	124.4 (3)
C2—C3—H3	125.8	O1—C11—C8	112.9 (2)
N1—C4—C5	111.3 (2)	O1—C12—C13	107.1 (3)
N1—C4—H4A	109.4	O1—C12—H12A	110.3
C5—C4—H4A	109.4	C13—C12—H12A	110.3
N1—C4—H4B	109.4	O1—C12—H12B	110.3
C5—C4—H4B	109.4	C13—C12—H12B	110.3
H4A—C4—H4B	108.0	H12A—C12—H12B	108.5
C10—C5—C6	119.0 (2)	C12—C13—H13A	109.5
C10—C5—C4	120.7 (2)	C12—C13—H13B	109.5
C6—C5—C4	120.3 (2)	H13A—C13—H13B	109.5
C5—C6—C7	120.4 (2)	C12—C13—H13C	109.5
C5—C6—H6	119.8	H13A—C13—H13C	109.5
C7—C6—H6	119.8	H13B—C13—H13C	109.5
C8—C7—C6	120.4 (2)	C3—N1—N2	110.7 (3)
C8—C7—H7	119.8	C3—N1—C4	127.7 (2)
C6—C7—H7	119.8	N2—N1—C4	121.4 (2)
C7—C8—C9	119.2 (2)	C1—N2—N1	104.3 (2)
C7—C8—C11	122.5 (2)	C11—O1—C12	117.0 (2)
C9—C8—C11	118.3 (2)

N2—C1—C2—C3	−0.8 (4)	C7—C8—C11—O2	−178.2 (3)
C1—C2—C3—N1	0.6 (4)	C9—C8—C11—O2	1.1 (4)
N1—C4—C5—C10	−88.7 (3)	C7—C8—C11—O1	1.5 (4)
N1—C4—C5—C6	89.5 (3)	C9—C8—C11—O1	−179.2 (2)
C10—C5—C6—C7	1.8 (4)	C2—C3—N1—N2	−0.3 (4)
C4—C5—C6—C7	−176.5 (2)	C2—C3—N1—C4	174.4 (3)
C5—C6—C7—C8	0.2 (4)	C5—C4—N1—C3	−89.3 (4)
C6—C7—C8—C9	−2.0 (4)	C5—C4—N1—N2	84.9 (3)
C6—C7—C8—C11	177.3 (2)	C2—C1—N2—N1	0.6 (4)
C7—C8—C9—C10	1.6 (4)	C3—N1—N2—C1	−0.2 (3)
C11—C8—C9—C10	−177.7 (2)	C4—N1—N2—C1	−175.3 (2)
C6—C5—C10—C9	−2.1 (4)	O2—C11—O1—C12	1.0 (4)
C4—C5—C10—C9	176.1 (2)	C8—C11—O1—C12	−178.7 (2)
C8—C9—C10—C5	0.4 (4)	C13—C12—O1—C11	−175.4 (3)

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/N2/C1–C3 and C5–C10 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg2ⁱ	0.93	2.94	3.670 (4)	137
C4—H4A···Cg1ⁱⁱ	0.97	3.00	3.600 (3)	122
C12—H12A···Cg2ⁱⁱⁱ	0.97	2.82	3.689 (4)	150

Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

Cg1 and Cg2 are the centroids of the N1/N2/C1–C3 and C5–C10 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2···Cg2ⁱ	0.93	2.94	3.670 (4)	137
C4—H4A···Cg1ⁱⁱ	0.97	3.00	3.600 (3)	122
C12—H12A···Cg2ⁱⁱⁱ	0.97	2.82	3.689 (4)	150

Symmetry codes: (i) x−1, y, z; (ii) −x, −y, −z; (iii) −x, −y+1, −z+1.

Acknowledgements

We are grateful for financial support from the National Natural Science Foundation of China (No. 81302644) and Jiangsu Ainaji Neo Energy Science & Technology Co. Ltd (No. 8507040091).

References

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